NO137789B - FENDER DEVICE. - Google Patents
FENDER DEVICE. Download PDFInfo
- Publication number
- NO137789B NO137789B NO98/72A NO9872A NO137789B NO 137789 B NO137789 B NO 137789B NO 98/72 A NO98/72 A NO 98/72A NO 9872 A NO9872 A NO 9872A NO 137789 B NO137789 B NO 137789B
- Authority
- NO
- Norway
- Prior art keywords
- titanium tetrachloride
- sludge
- vanadium
- treated
- recovered
- Prior art date
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 74
- 239000010802 sludge Substances 0.000 claims description 54
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 19
- 150000003682 vanadium compounds Chemical class 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 238000009835 boiling Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 4
- 235000021323 fish oil Nutrition 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- -1 VOC^ Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 101100497923 Viola odorata Voc1 gene Proteins 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010405 reoxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02B—HYDRAULIC ENGINEERING
- E02B3/00—Engineering works in connection with control or use of streams, rivers, coasts, or other marine sites; Sealings or joints for engineering works in general
- E02B3/20—Equipment for shipping on coasts, in harbours or on other fixed marine structures, e.g. bollards
- E02B3/26—Fenders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
Description
Fremgangsmåte ved rensning av titantetraklorid. Procedure for purification of titanium tetrachloride.
Foreliggende oppfinnelse angår en The present invention relates to a
fremgangsmåte ved rensning av teknisk titantetraklorid til en kvalitet egnet for fremstilling av titanmetall, -pigmenter og method for purifying technical titanium tetrachloride to a quality suitable for the production of titanium metal, pigments and
-forbindelser. -connections.
Titantetraklorid fremstilles vanligvis Titanium tetrachloride is usually prepared
ved klorering av titanholdige jernmalmer eller rutil. Det er alltid forurenset av forskjellige forbindelser som er blitt dannet under kloreringen og/eller ført over fra kloreringsovnen sammen med det damp-formige titantetraklorid. Forurensningene innbefatter klorider av metaller som er til-stede i malmen i små mengder, støv og andre fremmedlegemer suspendert i strøm-men av titantetrakloriddamp, samt andre urenheter tatt opp under kloreringen. Flere av disse forurensningene kan skilles ut ved fraksjonert destillasjon. Imidlertid by chlorination of titanium-containing iron ores or rutile. It is always contaminated by various compounds that have been formed during the chlorination and/or carried over from the chlorination furnace together with the vaporous titanium tetrachloride. The contaminants include chlorides of metals which are present in the ore in small quantities, dust and other foreign bodies suspended in the stream of titanium tetrachloride vapor, as well as other impurities taken up during the chlorination. Several of these pollutants can be separated by fractional distillation. However
er det flere forbindelser, spesielt vanadiumforbindelser, og fremfor alt VOCls, som ikke lett lar seg skille på dette vis fordi deres kokepunkt ligger for nær titantetrakloridets kokepunkt. there are several compounds, especially vanadium compounds, and above all VOCls, which cannot be easily separated in this way because their boiling point is too close to the boiling point of titanium tetrachloride.
Det benyttes derfor ofte en kjemisk A chemical is therefore often used
behandling for å felle slike forurensninger i form av uoppløselige forbindelser, som så lettere lar seg fjerne fra titantetrakloridet, hvorved dette blir renset. Den reaksjon som finner sted ved rensning av teknisk titantetraklorid med egnede behandlingsmidler, er ikke entydig klarlagt. Imidlertid antas det at behandlingsmidlene først og fremst virker som reduksjonsmidler og reduserer vanadiumoksyklorid, VOCln, til forbindelser som VOC^, som felles ut som uopp-løselige forbindelser. De reduserte, uopp-løselige vanadiumforbindelser kan lett skilles fra det behandlete titantetraklorid som treatment to trap such impurities in the form of insoluble compounds, which can then be more easily removed from the titanium tetrachloride, whereby this is purified. The reaction that takes place during the purification of technical titanium tetrachloride with suitable treatment agents is not unequivocally clarified. However, it is believed that the treatment agents primarily act as reducing agents and reduce vanadium oxychloride, VOCln, to compounds such as VOC^, which precipitate as insoluble compounds. The reduced, insoluble vanadium compounds can be easily separated from the treated titanium tetrachloride which
så kan underkastes fraksjonert destillasjon then can be subjected to fractional distillation
for fremstilling av raffinert titantetraklorid med ønsket renhet. For å oppnå fullstendig utskillelse av uønskede vanadiumforbindelser, innbefattet VOCl3, har det for the production of refined titanium tetrachloride of the desired purity. To achieve complete separation of unwanted vanadium compounds, including VOCl3, it has
hittil normalt vært nødvendig å benytte until now normally been necessary to use
et betraktelig overskudd av slike kjemiske a considerable excess of such chemical
behandlingsmidler utover den mengde som teoretisk skulle trenges. treatment agents beyond the quantity that would theoretically be needed.
Foreliggende oppfinnelse tar sikte på å tilveiebringe en mer effektiv og økonom-isk fremgangsmåte for rensning av titantetraklorid. The present invention aims to provide a more efficient and economical method for purifying titanium tetrachloride.
Ifølge oppfinnelsen behandles vanadiumholdig, teknisk titantetraklorid med et According to the invention, vanadium-containing, technical titanium tetrachloride is treated with a
reduksjonsmiddel for utfelling av uopp-løselig vanadiumforbindelser, som skilles fra det behandlede titantetraklorid i form av et titantetrakloridholdig slam. Slammet varmes så opp for å drive av og gjenvinne dets innhold av titantetraklorid, som siden reducing agent for precipitation of insoluble vanadium compounds, which are separated from the treated titanium tetrachloride in the form of a titanium tetrachloride-containing sludge. The sludge is then heated to drive off and recover its titanium tetrachloride content, such as silk
kan blandes med ytterligere teknisk titantetraklorid som skal renses. Etter at slammet er skilt fra det behandlede titantetraklorid og inntil dets innhold av titantetraklorid er gjenvunnet, holdes slammet under en ikke-oksyderende gaissatmosfære. can be mixed with additional technical titanium tetrachloride to be purified. After the sludge is separated from the treated titanium tetrachloride and until its titanium tetrachloride content is recovered, the sludge is kept under a non-oxidizing gas atmosphere.
Uttrykket «gassatmosfære» er brukt for å betegne en atmosfære som i det vesentlige består av et eller flere media som er gasser The term "gas atmosphere" is used to denote an atmosphere that essentially consists of one or more media that are gases
ved værelsestemperatur og normalt trykk og innebefatter derfor ikke en titantetra-kloridatmosf ære. at room temperature and normal pressure and therefore does not contain a titanium tetrachloride atmosphere.
Det har vist seg at selvom vanadiumoksyklorid, VOCl3, lett kan felles i form av en uoppløselig forbindelse fra teknisk titantetraklorid ved behandling med et reduksjonsmiddel, vil den utfelte forbindelse reoksyderes under iallfall delvis gjendan-neise av uønsket VOC1,, dersom slam med slike uoppløselige forbindelser utsettes for oksygen. Av denne grunn behandles slammet inneholdende de utfelte vanadiumforbindelser fra det øyeblikk slammet blir skilt fra det behandlede titantetraklorid og til dets innhold av titantetraklorid er gjenvunnet hele tiden under betingelser som utelukker reoksydering av de utfelte vanadiumforbindelser til VOC1.,. Ifølge foreliggende oppfinnelse kan dette oppnås ved å påse at en ikke-oksyderende gassatmosfære, som en inert gass, fortrinsvis helium eller argon, opprettholdes over slammet så lenge dette er under behandling. It has been shown that although vanadium oxychloride, VOCl3, can easily be precipitated in the form of an insoluble compound from technical titanium tetrachloride by treatment with a reducing agent, the precipitated compound will be reoxidized with at least partial recovery of unwanted VOC1, if sludge with such insoluble compounds exposed to oxygen. For this reason, the sludge containing the precipitated vanadium compounds is treated from the moment the sludge is separated from the treated titanium tetrachloride and until its content of titanium tetrachloride is recovered all the time under conditions that exclude reoxidation of the precipitated vanadium compounds to VOC1.,. According to the present invention, this can be achieved by ensuring that a non-oxidizing gas atmosphere, such as an inert gas, preferably helium or argon, is maintained over the sludge as long as it is being treated.
Reduksjonsmidlet som brukes ved behandlingen av teknisk titantetraklorid ved foreliggende fremgangsmåte, kan være et hvilket som helst av de hittil kjente behandlingsmidler benyttet for dette formål. Disse omfatter metallisk kobber, titantri-klorid, hydrogen, reaktive sulfider som H2S, kullstoffholdige organiske forbindelser og forskjellige mineralske, animalske og vegetabilske oljer. Da flere av disse så-kalte behandlingsmidler frembringer en polymer- eller kullstoffholdig avsetning, et kompleks eller en fysikalsk forbindelse med vanadiumforbindelsene under rensningen, antas det at behandlingsmidlene i første rekke reduserer tilstedeværende VOCL, under dannelse av en uoppløselig forbindelse. The reducing agent used in the treatment of technical titanium tetrachloride in the present method can be any of the previously known treatment agents used for this purpose. These include metallic copper, titanium trichloride, hydrogen, reactive sulphides such as H2S, carbonaceous organic compounds and various mineral, animal and vegetable oils. As several of these so-called treatment agents produce a polymer or carbonaceous deposit, a complex or a physical compound with the vanadium compounds during the cleaning, it is assumed that the treatment agents primarily reduce the VOCL present, forming an insoluble compound.
Behandlingen kan utføres ved en hvil-ken som helst ønsket temperatur. Fortrinnsvis settes reduksjonsmidlet til det flytende, tekniske TiCl,, og blandingen om-røres og varmes til en temperatur nær titantetrakloridets kokepunkt. Etter at opp-varmningen og omrøringen har pågått en stund, kan den utfelte, uoppløselige vana-diumforbindelse lett skilles fra det behandlede TiCl,. Dette kan gjøres ved bunnfel-ling og dekantering, ved filtrering, eller fortrinnsvis ved å destillere av det behandlede TiCl, slik at det blir igjen et slam inneholdende det uoppløselige vanadium. Separeringen bør utføres slik at slammet inneholder en viss mengde tilbakeholdt TiCl,, først og fremst for å lette behandlingen av slammet i pumper og rørledninger. Slammet bør selvfølgelig ikke inneholde mer TiCl, enn hva som er ønskelig eller nødvendig, og TiCl-iranhoIdet i stemme* kan variere fra ca. 5% til 25 %. Slammet overføres deretter til en koker for gjen-vinning av dets TiCl,-innhold. Det kan selv-følgelig mellomlagres under overføringen dersom ønsket. Slammet behandles fortrinnsvis satsvis i en passende koker hvor slammet med letthet kan bringes til en temperatur over titantetrakloridets kokepunkt. I slamkokeren blir TiCl, destillert av og gjenvunnet og, dersom ønsket, kon-densert og tilbakeført for blanding med ytterligere teknisk, vanadiumholdig TiCl, som skal renses. De beste resultater oppnås dersom slamkokeren holdes på en temperatur mellom ca. 136° C og 200° C slik at innholdet av TiCl., effektivt kan skilles av og gjenvinnes, samtidig som de faste stof-fer i slammet tørkes så å si fullstendig. The treatment can be carried out at any desired temperature. Preferably, the reducing agent is added to the liquid technical TiCl, and the mixture is stirred and heated to a temperature close to the boiling point of titanium tetrachloride. After the heating and stirring have continued for some time, the precipitated, insoluble vanadium compound can be easily separated from the treated TiCl,. This can be done by sedimentation and decantation, by filtration, or preferably by distilling the treated TiCl, so that a sludge containing the insoluble vanadium remains. The separation should be carried out so that the sludge contains a certain amount of retained TiCl, primarily to facilitate the treatment of the sludge in pumps and pipelines. The sludge should of course not contain more TiCl than is desirable or necessary, and the TiCl-iranhoId in voice* can vary from approx. 5% to 25%. The sludge is then transferred to a digester for recovery of its TiCl 2 content. It can therefore be temporarily stored during the transfer if desired. The sludge is preferably treated in batches in a suitable digester where the sludge can easily be brought to a temperature above the boiling point of titanium tetrachloride. In the sludge digester, TiCl is distilled off and recovered and, if desired, condensed and returned for mixing with further technical, vanadium-containing TiCl, which is to be purified. The best results are achieved if the sludge digester is kept at a temperature between approx. 136° C and 200° C so that the content of TiCl. can be effectively separated and recovered, while the solids in the sludge are dried, so to speak, completely.
Titantetrakloridet som er gjenvunnet fra slammet, blandes med ytterligere teknisk titantetraklorid som skal renses. Selvom det har et lavt vanadiuminnhold, vil det som regel inneholde andre forurensninger som aluminiumklorid, klorerte organiske forbindelser og andre uønskede be-standdeler. Som tidligere nevnt kan det i praksis blandes med teknisk titantetraklorid før dette behandles med reduksjonsmiddel. Det gjenvundne titantetraklorid fører så å si ingen ytterligere vanadium-fOTurensning med seg, og det ledes inn i strømmen av TiCl4-damp og passerer så ganske enkelt gjennom den alminnelige renseprosess. Om ønskes kan imidlertid det gjenvundne titantetraklorid blandes med teknisk titantetraklorid på et hvilket som helst trinn under prosessen som sikrer at det blir renset for de spesielle urenheter som det inneholder. The titanium tetrachloride recovered from the sludge is mixed with additional technical titanium tetrachloride to be purified. Although it has a low vanadium content, it will usually contain other contaminants such as aluminum chloride, chlorinated organic compounds and other undesirable components. As previously mentioned, it can in practice be mixed with technical titanium tetrachloride before this is treated with a reducing agent. The recovered titanium tetrachloride carries with it virtually no further vanadium-foot purification, and is introduced into the stream of TiCl4 vapor and then simply passes through the general purification process. However, if desired, the recovered titanium tetrachloride can be mixed with technical titanium tetrachloride at any stage during the process which ensures that it is purified of the special impurities it contains.
Ifølge foreliggende fremgangsmåte blir slammet fra det skilles fra det behandlede According to the present method, the sludge from it is separated from the treated
titantetraklorid og inntil dets innhold av titantetraklorid er gjenvunnet, hele tiden behandlet under omgivelser som ikke inneholder en oksyderende gass som f. eks. luft. Dette kan oppnås ved å opprettholde en atmosfære av inert gass, som helium eller argon, på alle steder hvor slammet ellers ville blitt utsatt for kontakt med luft. En ureaktiv gassatmosfære opprettholdes så-ledes over slammet i alle tanker, oppbevar-ingskar og behandlingsapparater, deriblant slamkokeren. Det er klart at en apparatur som er fullstendig fylt av slammet slik at det ikke er noen atmosfære eller tomrom over dette, vil være tilstrekkelig til å hindre kontakt med en oksygenholdig gass. På denne måte forhindres vanadiumforbindelsene i slammet fra reoksydering og gjendannelse av det opprinnelige, uønskede VOCl„ samtidig som det gjenvundne TiCl^ fra slammet er så å si rent for oppløste vanadiumforbindelser. titanium tetrachloride and until its content of titanium tetrachloride is recovered, all the time treated under an environment that does not contain an oxidizing gas such as e.g. air. This can be achieved by maintaining an atmosphere of inert gas, such as helium or argon, in all places where the sludge would otherwise be exposed to contact with air. A non-reactive gas atmosphere is thus maintained above the sludge in all tanks, storage vessels and treatment devices, including the sludge digester. It is clear that an apparatus which is completely filled with the sludge so that there is no atmosphere or void above it will be sufficient to prevent contact with an oxygen-containing gas. In this way, the vanadium compounds in the sludge are prevented from reoxidation and regeneration of the original, unwanted VOCl„, while the recovered TiCl^ from the sludge is, so to speak, clean of dissolved vanadium compounds.
Eksempel 1: Example 1:
En sats med teknisk titantetraklorid inneholdende 0,7% vanadium i form av VOCl3 basert på titaninnholdet, ble behandlet med 0,18 % H2S i en lukket tank utstyrt med en rører. Etter omrøring av blandingen av H2S og TiCl4 i 30 minutter ved en temperatur på 120° C ble tempera-turen i tanken hevet til kokepunktet for TiCl^ og det behandlede TiCl, destillert av inntil et slam inneholdende 20 % TiCl, ble igjen på bunnen av tanken. Tanken ble deretter fylt med helium og varmetilførse-len avstengt for å hindre videre destillasjon av TiCl,. A batch of technical titanium tetrachloride containing 0.7% vanadium in the form of VOCl3 based on the titanium content was treated with 0.18% H2S in a closed tank equipped with a stirrer. After stirring the mixture of H2S and TiCl4 for 30 minutes at a temperature of 120°C, the temperature in the tank was raised to the boiling point of TiCl^ and the treated TiCl distilled off until a sludge containing 20% TiCl remained at the bottom of the idea. The tank was then filled with helium and the heat supply shut off to prevent further distillation of TiCl.
Det behandlede TiCl, ble fraksjonsde-stillert, og ved analyse ble det funnet at det avdestillerte TiCl4 inneholdt under 0,01 % vanadium bergenet på titaninnholdet. Det avdestillerte TiCl, hadde en renhet som gjorde det egnet for bruk ved fremstilling av titanmetall. The treated TiCl was fractionally distilled, and by analysis it was found that the distilled TiCl4 contained less than 0.01% of the vanadium bergene on the titanium content. The distilled TiCl had a purity that made it suitable for use in the production of titanium metal.
Slammet ble overført til en beholder som på forhånd var fylt med helium, og deretter til en slamkoker også med heliumatmosfære. Slammet ble oppvarmet til en temperatur på ca. 180° C for å drive av TiCl,, samtidig som det ble igjen en tørr rest. The sludge was transferred to a container that was previously filled with helium, and then to a sludge digester also with a helium atmosphere. The sludge was heated to a temperature of approx. 180° C to drive off TiCl, while leaving a dry residue.
Ved analyse viste det seg at det TiCl4 som var blitt gjenvunnet fra slammet, inneholdt mindre enn 0,02 % vanadium. Det ble blandet med teknisk, vanadiumholdig TiCl4 som skulle behandles med H.,S. On analysis, the TiCl4 recovered from the sludge was found to contain less than 0.02% vanadium. It was mixed with technical, vanadium-containing TiCl4 which was to be treated with H.,S.
Eksempel 2: Example 2:
Teknisk titantetraklorid av samme sort som benyttet i eksempel 1 ble underkastet samme behandling med hydrogensulfid som i eksempel 1, og det behandlede titantetraklorid ble destillert av inntil et slam inneholdende ca. 20% TiCl, ble igjen på bunnen av tanken. Tanken ble deretter fylt med hydrogen og varmetilførselen avstengt for å hindre videre destillasjon av TiCl4. Technical titanium tetrachloride of the same variety as used in example 1 was subjected to the same treatment with hydrogen sulphide as in example 1, and the treated titanium tetrachloride was distilled off until a sludge containing approx. 20% TiCl, remained at the bottom of the tank. The tank was then filled with hydrogen and the heat supply turned off to prevent further distillation of TiCl4.
Det behandlede TiCl4 ble fraksjonert og en analyse viste at det avdestillerte TiCl, inneholdt under 0,01 % vanadium be-regnet på titaninnholdet. The treated TiCl4 was fractionated and an analysis showed that the distilled TiCl contained less than 0.01% vanadium calculated on the titanium content.
Slammet ble som i eksempel 1, over-ført til og oppbevart på en beholder som i dette tilfelle på forhånd var fylt med hydrogen, og slammet ble senere overført til en slamkoker også inneholdende en hy-drogenatmosfære. Slammet ble som i eksempel 1, oppvarmet i slamkokeren for å drive av TiCl, slik at det ble igjen en tørr rest. As in example 1, the sludge was transferred to and stored in a container which in this case was previously filled with hydrogen, and the sludge was later transferred to a sludge digester also containing a hydrogen atmosphere. As in example 1, the sludge was heated in the sludge digester to drive off the TiCl, so that a dry residue remained.
Analyse av det titantetraklorid som ble gjenvunnet fra slammet, viste at det også i dette tilfelle inneholdt mindre enn 0,02 % vanadium, og det ble derfor blandet med det tekniske titantetraklorid som skulle renses. Analysis of the titanium tetrachloride that was recovered from the sludge showed that it also contained less than 0.02% vanadium, and it was therefore mixed with the technical titanium tetrachloride that was to be purified.
Eksempel 3: Example 3:
Teknisk titantetraklorid av samme sort som benyttet i eksempel 1, ble behandlet under de samme betingelser med 0,1 % fiskeolje med et jodtall på ca. 190. Det behandlede TiCl4 viste, etter å ha vært underkastet en fraksjonert destillasjon, samme renhet som oppnådd i eksempel 1. Slammet ble behandlet i slamkokeren under en heliumatmosfære som tidligere beskrevet, og det gjenvundne TiCl4 viste et vanadiuminnhold på under 0,01 %. Det hadde samme kvalitet som titantetrakloridet gjenvunnet i eksempel 1, og var egnet for blanding med teknisk titantetraklorid som skulle reduksjonsbehandles. Technical titanium tetrachloride of the same variety as used in example 1 was treated under the same conditions with 0.1% fish oil with an iodine value of approx. 190. The treated TiCl4 showed, after being subjected to a fractional distillation, the same purity as obtained in Example 1. The sludge was treated in the sludge digester under a helium atmosphere as previously described, and the recovered TiCl4 showed a vanadium content of less than 0.01%. It had the same quality as the titanium tetrachloride recovered in example 1, and was suitable for mixing with technical titanium tetrachloride which was to be reduced.
Eksempel 4: Example 4:
Teknisk titantetraklorid av samme sort som brukt i de forangående eksempler ble behandlet med 0,1 % fiskeolje som i eksempel 3. I dette tilfelle ble slammet såvel i destillasjonstanken, som i oppbevarings-beholderen og i slamkokeren holdt under en nitrogenatmosfære for å hindre reoksy-dasjon av vanadiumforbindelsene. Det fra slammet gjenvundne titantetraklorid hadde igjen et vanadiuminnhold på under 0,02 % og ble ført tilbake i prosessen. Technical titanium tetrachloride of the same type as used in the previous examples was treated with 0.1% fish oil as in example 3. In this case, the sludge in the distillation tank, as well as in the storage container and in the sludge digester was kept under a nitrogen atmosphere to prevent reoxygenation. dation of the vanadium compounds. The titanium tetrachloride recovered from the sludge again had a vanadium content of less than 0.02% and was fed back into the process.
Til sammenligning ble en sats teknisk TiCl4 av samme sort som benyttet i eksem-plene 1—4, behandlet med 0,1 % fiskeolje og det behandlede TiCl, avdestillert. Der-på ble slammet, som inneholdt 20 % TiCl4, overført fra behandlingstanken til en åpen beholder, utsatt for luft i 15 dager og fylt i slamkokeren som ikke hadde noen be-skyttende, ureaktiv gaissatmosfære. Titantetrakloridet som ble gjenvunnet under disse betingelser, inneholdt 0,47 % vanadium basert på titaninnholdet. Dette viser at en vesentlig del av de reduserte vanadiumforbindelser i slammet var blitt oksydert under gjendannelse av VOCl3 som ble destillert av samtidig med det gjenvundne TiCl4. En tilsetning av TiCl4 gjenvunnet under disse betingelser til teknisk TiCl4 ville kreve en ekstra mengde fiskeolje eller et annet reduksjonsmiddel for å dekke innholdet av vanadiumforurensninger tilført ved det gjenvundne TiCl,. Det samme forhold gjorde seg gjeldende ved bruk av H.2S som behandlingsmiddel, og etter at slammet var blitt utsatt for kontakt med luft i 5 dager, viste det gjenvundne TiCl, et vanadiuminnhold på 0,217 %. For comparison, a batch of technical TiCl4 of the same type as used in examples 1-4, treated with 0.1% fish oil and the treated TiCl, was distilled off. The sludge, which contained 20% TiCl4, was then transferred from the treatment tank to an open container, exposed to air for 15 days and filled into the sludge digester which had no protective, non-reactive gas atmosphere. The titanium tetrachloride recovered under these conditions contained 0.47% vanadium based on the titanium content. This shows that a substantial part of the reduced vanadium compounds in the sludge had been oxidized during the recovery of VOCl3, which was distilled off at the same time as the recovered TiCl4. An addition of TiCl4 recovered under these conditions to technical TiCl4 would require an additional amount of fish oil or other reducing agent to cover the content of vanadium impurities added by the recovered TiCl4. The same condition applied when using H.2S as a treatment agent, and after the sludge had been exposed to air for 5 days, the recovered TiCl showed a vanadium content of 0.217%.
Dersom slammet behandles og TiCl4 gjenvinnes fra slammet ved en fremgangsmåte som beskrevet, samtidig med at slammet utsettes for kontakt med luft eller andre oksygenholdige gasser, er det blitt fastslått at vanadiumforbindelsene da vil reoksydere til oppløselig vanadiumoksyklorid, VOCLj, som vil foreligge i titantetrakloridet gjenvunnet fra slammet. Når dette forurensede, gjenvundne titantetraklorid blir satt til teknisk, vanadiumholdig TiCl4, vil det tekniske TiCl4 kreve adskillig mer reduksjonsmiddel for effektiv felling av vanadiumet enn dersom titantetrakloridet gjenvunnet fra slammet er praktisk fritt for vanadium. Foreliggende fremgangsmåte muliggjør derfor bruk av en mindre mengde reduksjonsmiddel ved behandling av det tekniske titantetraklorid, idet ytterligere forurensning fra gjenvunnet titantetraklorid ikke behøver å fjernes. Foreliggende fremgangsmåte er dessuten for-delaktig ved at behandlingen lettere kan kontrolleres og den nødvendige mengde reduksjonsmiddel mer nøyaktig forutsis, idet bare de forurensninger som foreligger i det tekniske titantetraklorid behøver å tas i betraktning. Under de beskrevne forhold kan hele prosessen gjennomføres meget effektivt, og de utfelte vanadiumforbindelser blir fullstendig fjernet ved uttømming av de faste stoffene fra slamkokeren, hvor- If the sludge is treated and TiCl4 is recovered from the sludge by a method as described, at the same time that the sludge is exposed to contact with air or other oxygen-containing gases, it has been determined that the vanadium compounds will then reoxidize to soluble vanadium oxychloride, VOCLj, which will be present in the titanium tetrachloride recovered from the mud. When this contaminated, recovered titanium tetrachloride is added to technical, vanadium-containing TiCl4, the technical TiCl4 will require considerably more reducing agent for effective precipitation of the vanadium than if the titanium tetrachloride recovered from the sludge is practically free of vanadium. The present method therefore enables the use of a smaller amount of reducing agent when treating the technical titanium tetrachloride, since further contamination from recovered titanium tetrachloride does not need to be removed. The present method is also advantageous in that the treatment can be more easily controlled and the required amount of reducing agent more accurately predicted, since only the impurities present in the technical titanium tetrachloride need to be taken into account. Under the conditions described, the entire process can be carried out very efficiently, and the precipitated vanadium compounds are completely removed by draining the solids from the sludge digester, where
:ved en resirkulering eller økning av opp-løselig vanadiumoksyklorid i systemet unn-gås. : by recycling or increasing soluble vanadium oxychloride in the system is avoided.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB268571A GB1372058A (en) | 1971-01-19 | 1971-01-19 | Marine fender |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO137789B true NO137789B (en) | 1978-01-16 |
| NO137789C NO137789C (en) | 1978-04-26 |
Family
ID=9743992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO98/72A NO137789C (en) | 1971-01-19 | 1972-01-18 | FENDER DEVICE. |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US3890917A (en) |
| JP (1) | JPS5332596B1 (en) |
| AU (1) | AU450660B2 (en) |
| BE (1) | BE778224A (en) |
| BR (1) | BR7200320D0 (en) |
| CA (1) | CA951974A (en) |
| DE (1) | DE2202451C2 (en) |
| DK (1) | DK140347B (en) |
| ES (1) | ES398961A1 (en) |
| FR (1) | FR2122950A5 (en) |
| GB (1) | GB1372058A (en) |
| IT (1) | IT946722B (en) |
| NL (1) | NL170554C (en) |
| NO (1) | NO137789C (en) |
| SE (1) | SE395024B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO142486C (en) * | 1975-06-17 | 1980-08-27 | Irving Brummenaes | FENDER SYSTEM. |
| GB2165334B (en) * | 1984-10-08 | 1988-10-12 | Giken Kogyo Kk | Impact energy absorbing device for waterway walls |
| US4884919A (en) * | 1989-02-23 | 1989-12-05 | Moore Joe T | Pier cushioning system |
| DE102009043983B3 (en) * | 2009-09-11 | 2011-02-03 | Friedrich Wirz | Method for storage of ship in harbor wall, involves expanding hollow body in its circumference, where hollow body is provided for holding distance between ship and harbor wall at normal pressure or by holding pressure in resting state |
| US9038556B2 (en) * | 2011-12-14 | 2015-05-26 | Mehmet Nevres ULGEN | Fender assembly for boats |
| PL2929091T3 (en) * | 2012-12-10 | 2018-03-30 | KADEBY, Nils-Åke | Hydraulic fender apparatus |
| CN110091967B (en) * | 2019-04-30 | 2020-06-12 | 江苏赛尔橡胶股份有限公司 | But height-adjusting's rubber fender |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2039151A (en) * | 1932-02-15 | 1936-04-28 | S I M E C Soc Ind De Materiel | Device for cushioning the shock of ships |
| GB758566A (en) * | 1954-05-07 | 1956-10-03 | British Tanker Company Ltd | Improvements relating to fenders for jetties and the like |
| DE1209962B (en) * | 1961-10-17 | 1966-01-27 | Firestone Burleigh Marine Pneu | fender |
| US3106182A (en) * | 1961-10-17 | 1963-10-08 | Firestone Burleigh Marine Pneu | Fender |
-
1971
- 1971-01-19 GB GB268571A patent/GB1372058A/en not_active Expired
-
1972
- 1972-01-18 SE SE7200550A patent/SE395024B/en unknown
- 1972-01-18 AU AU38033/72A patent/AU450660B2/en not_active Expired
- 1972-01-18 NO NO98/72A patent/NO137789C/en unknown
- 1972-01-18 DK DK24072AA patent/DK140347B/en unknown
- 1972-01-18 ES ES398961A patent/ES398961A1/en not_active Expired
- 1972-01-18 CA CA132,660A patent/CA951974A/en not_active Expired
- 1972-01-19 BR BR320/72A patent/BR7200320D0/en unknown
- 1972-01-19 JP JP756272A patent/JPS5332596B1/ja active Pending
- 1972-01-19 BE BE778224A patent/BE778224A/en not_active IP Right Cessation
- 1972-01-19 DE DE2202451A patent/DE2202451C2/en not_active Expired
- 1972-01-19 NL NLAANVRAGE7200741,A patent/NL170554C/en not_active IP Right Cessation
- 1972-01-19 FR FR7201670A patent/FR2122950A5/fr not_active Expired
- 1972-01-19 IT IT19565/72A patent/IT946722B/en active
-
1973
- 1973-12-20 US US426697A patent/US3890917A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| IT946722B (en) | 1973-05-21 |
| SE395024B (en) | 1977-07-25 |
| DE2202451A1 (en) | 1972-09-07 |
| FR2122950A5 (en) | 1972-09-01 |
| ES398961A1 (en) | 1974-10-16 |
| NL170554B (en) | 1982-06-16 |
| AU450660B2 (en) | 1974-07-18 |
| NL170554C (en) | 1982-11-16 |
| CA951974A (en) | 1974-07-30 |
| JPS5332596B1 (en) | 1978-09-08 |
| GB1372058A (en) | 1974-10-30 |
| US3890917A (en) | 1975-06-24 |
| BR7200320D0 (en) | 1973-07-03 |
| DK140347C (en) | 1980-01-21 |
| BE778224A (en) | 1972-05-16 |
| DE2202451C2 (en) | 1982-05-06 |
| DK140347B (en) | 1979-08-06 |
| NO137789C (en) | 1978-04-26 |
| NL7200741A (en) | 1972-07-21 |
| AU3803372A (en) | 1973-07-19 |
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